Method of manufacturing group III nitride substrate and semiconductor device

ABSTRACT

The present invention provides a method of manufacturing a Group III nitride substrate that has less variations in in-plane carrier concentration and includes crystals grown at a high growth rate. The manufacturing method of the present invention includes: (i) forming a semiconductor layer (a seed layer 12) on a substrate, with the semiconductor layer being formed of a semiconductor expressed by a composition formula of Al u Ga v In 1−u−v N (wherein 0≦u≦1 and 0≦v≦1) and having a (0001) plane present at its surface; (ii) processing the surface of the semiconductor layer so that the surface becomes a plane sloped with respect to the (0001) plane of the semiconductor layer; and (iii) bringing the surface of the semiconductor layer into contact with a melt containing a solvent and at least one Group III element selected from gallium, aluminum, and indium, in an atmosphere containing nitrogen, to make the at least one Group III element and the nitrogen react with each other to grow Group III nitride crystals (GaN single crystals 13) on the semiconductor layer.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Division of application Ser. No. 10/757,864, filedJan. 15, 2004, which application is incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to a Group III nitride substrate(a substrate containing Group III nitride crystals), a method ofmanufacturing the same, and a semiconductor device.

2. Related Background Art

A Group III nitride compound semiconductor such as, for instance,gallium nitride (GaN) (hereinafter also referred to as a “Group IIInitride semiconductor” or a “GaN-based semiconductor”) has been gainingattention as a material for semiconductor elements that emit blue orultraviolet light. A blue laser diode (LD) is used for high-densityoptical disk devices or displays while a blue light emitting diode (LED)is used for displays, lighting, etc. It is expected to use anultraviolet LD in the field of biotechnology or the like and to use anultraviolet LED as an ultraviolet source for a fluorescent lamp.

Generally, substrates of a Group III nitride semiconductor (for example,GaN) that are used for LDs or LEDs are formed through vapor phaseepitaxy. For instance, substrates have been used that are obtainedthrough heteroepitaxial growth of Group III nitride crystals on asapphire substrate. However, the sapphire substrate and GaN crystals aredifferent from each other in lattice constant by 13.8% and incoefficient of linear expansion by 25.8%. Hence, a sufficiently highcrystallinity cannot be obtained in the GaN thin film obtained throughthe vapor phase epitaxy. Generally, crystals obtained by this methodhave a dislocation density of 10⁸ cm⁻² to 10⁹ cm⁻² and thus thereduction in dislocation density has been an important issue. In orderto resolve this issue, efforts have been made to reduce the dislocationdensity and thereby, for example, an epitaxial lateral overgrowth (ELOG)method has been developed. With this method, the dislocation density canbe reduced to around 10⁵ cm⁻² to 10⁶ cm⁻², but its manufacturing processis complicated.

On the other hand, besides the vapor phase epitaxy, a method of carryingout crystal growth from the liquid phase also has been studied. However,since the equilibrium vapor pressure of nitrogen is at least 10000 atmat a melting point of a Group III nitride single crystal such as, forinstance, GaN or AlN, conventionally it has been understood that acondition of 8000 atm at 1200° C. is required for growing GaN fromliquid phase. In this connection, recently, it was made clear that GaNwas able to be synthesized at relatively low temperature and pressure,specifically, 750° C. and 50 atm, by using a Na flux.

Recently, single crystals with the maximum crystal size of about 1.2 mmare obtained by a method in which a mixture of Ga and Na is melted in anitrogen gas atmosphere containing ammonia at 800° C. and 50 atm, andthen the single crystals are grown for 96 hours using the melt (forinstance, JP2002-293696A).

Furthermore, another method also has been reported in which after a GaNcrystal layer is formed on a sapphire substrate by a metal organicchemical vapor deposition (MOCVD) method, single crystals are grown by aliquid phase epitaxy (LPE) method.

However, in order to manufacture semiconductor devices with excellentcharacteristics at low cost, it has been required to provide a method ofmanufacturing a Group III nitride substrate with a lower dislocationdensity than that of conventional one and a method of manufacturing aGroup III nitride substrate at lower cost. A method of growing nitridecrystals from liquid phase is expected to be a method that allows aGroup III nitride substrate with less defects to be obtained. However,considerable variations in crystallinity are caused depending on a seedcrystal to be used and on in-plane carrier concentration of the nitridesubstrate. Furthermore, the growth rate is not so high, which has been aproblem.

SUMMARY OF THE INVENTION

With such a situation in mind, the present invention is intended toprovide a Group III nitride substrate that has less variations inin-plane carrier concentration and includes Group III nitride crystalsgrown at a high growth rate, and to a method of manufacturing the same.

In order to achieve the aforementioned object, a Group III nitridesubstrate of the present invention includes: a substrate; asemiconductor layer formed on the substrate; and Group III nitridecrystals formed on the semiconductor layer, wherein the semiconductorlayer is formed of a semiconductor expressed by a composition formula ofAl_(u)Ga_(v)In_(1−u−v)N (wherein 0≦u≦1 and 0≦v≦1). A surface of thesemiconductor layer is a plane that is sloped in one direction andincludes steps of (0001) planes arranged step-wise. The plane sloped inone direction and the (0001) planes form an angle of at least 0.05°therebetween, and the Group III nitride crystals formed on thesemiconductor layer have variations in in-plane carrier concentrationthat are within a range of one fifth to five times a carrierconcentration mean value.

In the present invention, the “Group III nitride” denotes asemiconductor expressed by a composition formula ofAl_(x)Ga_(y)In_(1−x−y)N (wherein 0≦x≦1 and 0≦y≦1) unless otherwisespecified. In this connection, it is understood that a formula of0≦1−x−y≦1 is satisfied since the composition ratio can never be anegative value (the same applies to other composition formulae).

A manufacturing method of the present invention includes the steps of:(i) forming a semiconductor layer on a substrate, with the semiconductorlayer being formed of a semiconductor expressed by a composition formulaof Al_(u)Ga_(v)In_(1−u−v)N (wherein 0≦u≦1 and 0≦v≦1) and having a (0001)plane present at its surface; (ii) processing the surface of thesemiconductor layer so that the surface becomes a plane sloped withrespect to the (0001) plane of the semiconductor layer; and (iii)bringing the surface of the semiconductor layer into contact with a meltcontaining a solvent and at least one Group III element selected fromgallium, aluminum, and indium, in an atmosphere containing nitrogen, tomake the at least one Group III element and the nitrogen react with eachother to grow Group III nitride crystals on the semiconductor layer.

A semiconductor device of the present invention includes: a substrate;and a semiconductor element formed on the substrate, wherein thesubstrate is a Group III nitride substrate manufactured by theabove-mentioned manufacturing method of the present invention. Thesemiconductor element may be a laser diode or a light emitting diode.

The Group III nitride substrate of the present invention has lessvariations in carrier concentration, includes Group III nitride crystalsgrown at a high growth rate, and thus can be manufactured efficiently.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A (surface) and 1B (cross section) show conventional crystalgrowth; and FIGS. 1C and 1D show crystal growth according to an exampleof a manufacturing method according to the present invention.

FIG. 2 includes a cross-sectional view showing another example of amanufacturing method according to the present invention and an enlargedschematic view showing a surface structure obtained by the method.

FIGS. 3A to 3C are cross-sectional views illustrating steps of stillanother example of a manufacturing method according to the presentinvention.

FIG. 4 is a schematic view showing an example of a manufacturingapparatus used in the manufacturing method of the present invention.

FIG. 5A is a graph showing PL intensity of a GaN crystal obtained by aconventional method; and FIG. 5B is a graph showing PL intensity of aGaN crystal obtained by a still another example of the presentinvention.

FIGS. 6A to 6F are cross-sectional views showing steps of a furtherexample of a manufacturing method according to the present invention.

FIGS. 7A to 7D are cross-sectional views showing steps of yet anotherexample of a manufacturing method according to the present invention.

FIG. 8 is a schematic view showing another example of a manufacturingapparatus used in a manufacturing method of the present invention.

FIG. 9 is a cross-sectional view showing an example of a semiconductordevice according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

In the present invention, it is preferable that the variations inin-plane carrier concentration are as small as possible. However, thevariations are at least within a range of one fifth to five times thecarrier concentration mean value. The variations in in-plane carrierconcentration can be determined by, for example the following methodthat is described in J. Appl. Phys. 75(2), 15 Jan. 1994, pp.1098-1101.

-   (1) First, the relationship between the carrier concentration and    Raman spectrum is determined and then a regression formula or a    calibration curve is prepared. The regression formula or calibration    curve can be prepared based on the relationship between the carrier    concentration of a Group III nitride substrate that has been    subjected to hole measurement beforehand and its Raman spectrum.-   (2) Next, the mean value of the carrier concentrations of the Group    III nitride crystals is determined. Specifically, first of all,    beams of exciting light used in the Raman measurement are focused to    have a beam diameter of 10 to 100 μm and the Raman spectrum is    measured at 10 to 50 spots located at 1-mm intervals. Subsequently,    based on the Raman spectrum thus measured, the carrier    concentrations of the Group III nitride crystals are determined    using the regression formula or calibration curve and then the    average value thereof is determined.-   (3) Furthermore, the Raman spectrum is measured at an arbitrary spot    of the Group III nitride crystals and then the carrier concentration    thereof is determined. The arbitrary spot may be one of the 10 to 50    spots subjected to the measurement carried out for determined the    mean value.

The Raman measurement is not particularly limited but may be carried outby, for example, irradiating the Group III nitride crystals withpolarized light emitted from an argon ion laser with an emissionwavelength of 488 nm, at room temperature. In this connection, forexample, a double monochromator or photoelectric doubling tube can beused for the Raman measurement.

In the Group III nitride substrate of the present invention, it ispreferable that the Group III nitride crystals are formed through liquidphase epitaxy. This is because the liquid phase epitaxy allows the GroupIII nitride crystals to grow at a higher growth rate.

In the Group III nitride substrate of the present invention, it ispreferable that the plane sloped in one direction and the (0001) planesform an angle of 0.05° to 0.5° therebetween.

The semiconductor layer of the Group III nitride substrate is formed by,for example, vapor phase epitaxy. In this case, the semiconductor layerhas a thickness of, for instance, about 100 μm, and the plane that issloped and the (0001) planes form an angle of, for example, 0.5°therebetween in the Group III nitride substrate. However, it should beunderstood that when a thicker film is to be grown, the vapor phaseepitaxy also allows the angle formed between the plane that is slopedand the (0001) planes to be 0.5° or larger.

In the Group III nitride substrate of the present invention, it ispreferable that the surfaces of the Group III nitride crystals and the(0001) planes form an angle of 0.05° to 5° therebetween.

The Group III nitride crystals of the Group III nitride substrate areformed by, for example, liquid phase growth. In this case, the Group IIInitride crystals grow, for instance, up to about 2 to 3 mm. In thisGroup III nitride substrate, the surfaces of the Group III nitridecrystals and the (0001) planes form an angle of, for example, 5°therebetween. In this connection, it should be understood that in thecase of growing crystals having a thickness of 3 mm or thicker, theangle formed between the surfaces of the Group III nitride crystals andthe (0001) planes can be set at 0.5° or larger.

In the present invention, a surface of a Group III nitride substrate issloped by at least 0.05° with respect to a C-plane, where the C-plane isa plane perpendicular to a C-axis of the Group III nitride substrate. Inthe following, providing this slope sometimes is referred to asoffcutting. In other words, offcutting is to process the surface of theGroup III nitride substrate so as to form an angle sloped by at least0.05° from the C-plane, which is a plane perpendicular to the C-axis ofthe Group III nitride substrate.

In the Group III nitride substrate of the present invention, it ispreferable that the Group III nitride crystals are gallium nitridecrystals.

In the manufacturing method of the present invention, it is preferablethat the at least one Group III element is gallium and the Group IIInitride crystals are gallium nitride.

In the manufacturing method of the present invention, the Group IIInitride crystals are grown on the semiconductor layer preferably at agrowth rate of at least 20 μm/hr, and more preferably at 30 μm/hr to 50μm/hr.

In the manufacturing method of the present invention, the Group IIInitride crystals that have grown on the semiconductor layer havevariations in in-plane carrier concentration that are preferably withina range of one fifth to five times a carrier concentration mean value,more preferably one third to three times, and further preferably half totwice.

In the manufacturing method of the present invention, it is preferablethat the atmosphere containing nitrogen is a pressure atmosphere. Thepressure of the pressure atmosphere is, for example, in a range of 2 to100 atm and preferably 5 to 50 atm.

In the manufacturing method of the present invention, it is preferablethat the solvent is alkali metal. It also is preferable that the solventcontains alkaline-earth metal beside the alkali metal. Preferably, thealkali metal is at least one selected from a group consisting of sodium,lithium, and potassium. Furthermore, calcium is preferable as thealkaline-earth metal.

In the manufacturing method of the present invention, the method ofprocessing the semiconductor layer substrate in the step (ii) is notparticularly limited but is preferably polishing.

In the manufacturing method of the present invention, it is preferablethat the steps (i) and (ii) are carried out simultaneously. In thiscase, preferably the steps (i) and (ii) are carried out using atemperature gradient provided during crystal growth.

In the manufacturing method of the present invention, the substrate isnot particularly limited but preferably is made of sapphire.

Hereinafter, one example of the present invention is described. Themethod of the present invention is a method of manufacturing a substrateincluding Group III nitride crystals expressed by a composition formulaof Al_(x)Ga_(y)In_(1−x−y)N (wherein 0≦x≦1 and 0≦y≦1), such as GaN orAlGaN.

In this method, first, on a substrate is formed a semiconductor layerthat is formed of a semiconductor expressed by a composition formula ofAl_(u)Ga_(v)In_(1−u−v)N (wherein 0≦u≦1 and 0≦v≦1) and has a (0001) planepresent at its surface (Step (i)). Examples of the substrate to be usedinclude a sapphire substrate whose surface is a C-plane, a C-plane SiCsubstrate, a (111) plane GaAs or Si substrate, and a GaN substrateobtained by growing a thin film thereon. Furthermore, a substrate with astructure such as an ELOG structure also may be used as the substrate.The semiconductor layer is a crystal layer to serve as a seed crystal,and specifically, is formed of GaN or Al_(u)Ga_(1−u)N. Such asemiconductor layer can be formed by, for instance, a metal organicchemical vapor deposition (MOCVD) method, a molecular beam epitaxy (MBE)method, or a hydride vapor phase epitaxy (HVPE) method. In theabove-mentioned method, the surface of the semiconductor layer to beformed is a (0001) plane. This semiconductor layer serves as a seedcrystal to be used in the crystal growth step carried out later.

Next, the surface of the semiconductor layer is processed so as tobecome a plane sloped with respect to the (0001) plane of thesemiconductor layer to serve as a seed crystal (Step (ii)). Theprocessing can be carried out by, for example, polishing. Specifically,the processing can be carried out by, for example, mechanochemicalpolishing using an abrasive liquid containing diamond as an abrasive. Bysuch processing, the surface of the semiconductor layer becomes a planesloped with respect to the (0001) plane macroscopically (on the order ofmillimeters). Microscopically (at an atomic level), however, thissurface is a stepped surface with the (0001) plane being exposed asshown in the enlarged view in FIG. 2. Preferably, the surface observedmacroscopically (on the order of millimeters) and the (0001) plane forman angle of 0.05° to 0.520 therebetween.

Next, in an atmosphere containing nitrogen (preferably, a pressureatmosphere having a pressure of 100 atm or lower), the surface of thesemiconductor layer is brought into contact with a melt containing asolvent and at least one Group III element selected from gallium,aluminum, and indium and thereby the at least one Group III element andthe nitrogen are made to react with each other to grow Group III nitridecrystals on the semiconductor layer (Step (iii)). As the atmospherecontaining nitrogen there is used a nitrogen gas atmosphere, or anatmosphere of a mixed gas of nitrogen gas and ammonia. The atmospherehas a pressure of, for instance, 1 atm to 50 atm.

As the solvent can be used, for example, a flux of an alkali metal. Asthe alkali metal is used at least one selected from lithium, sodium, andpotassium, i.e. one of them or a mixture thereof. The solvent maycontain alkaline-earth metal such as Ca beside the alkali metal.

The Group III element to be used as a material is selected depending onthe type of crystals to be formed. This step (iii) makes it possible toform Group III nitride crystals expressed by a composition formula ofAl_(x)Ga_(y)In_(1−x−y)N (wherein 0≦x≦1 and 0≦y≦1, such as GaN orAl_(x)Ga_(1−x)N, by a liquid phase epitaxy method. Furthermore, afterthe Group III nitride crystals are grown, a part other than the GroupIII nitride crystals is removed by polishing or the like as required andthereby a substrate formed of Group III nitride crystals alone can beobtained.

In the method of the present invention, the surface of the seed crystallayer is processed into a stepped shape with the (0001) plane beingexposed. Consequently, abnormal growth can be prevented from occurringduring crystal growth. Furthermore, as compared to the case of using acommon seed crystal substrate, crystals with higher surface flatness canbe obtained.

Particularly, in the liquid phase epitaxy, the use of a substrate slopedin one direction makes it possible to improve the growth rate anduniformity in concentration of impurities introduced into the crystalsas compared to the case of using a substrate that is not sloped.

The Group III nitride substrate of the present invention is a substrateobtained by the above-mentioned manufacturing method. That is, itincludes: a substrate; a semiconductor layer formed on the substrate;and Group III nitride crystals formed on the semiconductor layer,wherein the semiconductor layer is formed of a semiconductor expressedby a composition formula of Al_(u)Ga_(v)In_(1−u−v)N (wherein 0≦u≦1 and0≦v≦1), a surface of the semiconductor layer that is in contact with theGroup III nitride crystals is a plane that is sloped in one directionand including steps of (0001) planes arranged step-wise. In thissubstrate, the Group III nitride crystals are, for example, galliumnitride.

Hereinafter, the present invention is described further in detail usingpracticable examples. The following examples are described with respectto the case of growing GaN crystals as an example. However, Group IIInitride crystals expressed by a composition formula ofAl_(x)Ga_(y)In_(1−x−y)N (wherein 0≦x≦1 and 0≦y≦1) such asAl_(x)Ga_(1 −x)N or AIN also can be formed by the similar method.

Example 1

In this example, the description is directed to a method includingdepositing GaN crystals on a sapphire substrate by a metal organicchemical vapor deposition (MOCVD) method, which then is used as a seedcrystal substrate, and growing single crystals by a liquid phase epitaxy(LEP) method using the seed crystal substrate. The present invention ischaracterized in that the surfaces of GaN crystals formed by depositionare processed to be sloped.

First, the seed crystal substrate is formed. FIG. 2 shows aconfiguration of this substrate. A substrate 10 includes a sapphiresubstrate 11 made of sapphire (crystalline Al₂O₃) and a seed layer 12made of GaN. In this connection, the seed layer 12 may contain aluminumor indium instead of gallium as a Group III element. In other words, theseed layer 12 is not limited as long as it is formed of Group IIInitride that satisfies a composition formula of Al_(u)Ga_(v)In_(1−u−v)N(wherein 0≦u ≦1 and 0≦v ≦1). The surface of the seed layer 12 is a planesloped from a (0001) plane.

A method of manufacturing the substrate 10 is described with referenceto FIGS. 3A to 3C. First, the temperature of the sapphire substrate 11is raised to be about 1020° C. to 1100° C., and then the seed layer 12is formed by the MOCVD method (FIG. 3A). Specifically, trimethylgallium(TMG) and ammonia (NH₃) are supplied onto the substrate to form the seedlayer 12 of GaN. In this connection, another method that allows a GroupIII nitride semiconductor to grow, such as, for instance, a hydridevapor phase epitaxy (HVPE) method or a molecular beam epitaxy (MBE)method, may be used.

The seed layer 12 has a thickness of, for example, 20 μm.Microscopically, the surface of the seed layer 12 includes concavitiesand convexities formed of steps as shown in the enlarged view in FIG.3A.

Next, in order to bring the crystal orientation at the surface of theGaN crystals (the seed layer 12) obtained in the above to be offcut, thesurface of the seed layer 12 is ground to be sloped (FIG. 3B). In thepresent example, mechanochemical polishing is carried out using anabrasive liquid containing diamond as an abrasive so that the surface issloped away from the (0001) plane by 0.1 degree. The offcut angle may beset depending on the thickness of the GaN film or the crystallinity of athin film of crystals to be grown later but is desirably around 0.05° to0.5°. Microscopically, the surface of the seed layer 12 of the substrateshown in FIG. 3B has a stepped shape as shown in FIG. 2. The size of theenlarge view in FIG. 2 is about 0.5 to 5 nm in length and about 1 to 5μm in width.

Using the seed crystal substrate thus obtained, GaN single crystals 13are grown as shown in FIG. 3C. A method for growing them is describedbelow.

FIG. 4 shows an example of an LPE apparatus (an electric furnace) usedin the method of the present invention. This LPE apparatus includes achamber 21 made of stainless steel and a furnace cover 22. The LPEapparatus is constructed to bear a pressure of 50 atm. Heaters 23 aredisposed inside the chamber 21. The chamber 21 is composed of threezones provided with thermocouples 24 a to 24 c, respectively. The threezones are controlled so as to keep their temperature within a range of±0.1° C., and thereby the temperature inside the furnace is controlledto be uniform. A core tube 25 is disposed to improve the uniformity ofthe temperature inside the furnace and to prevent impurities from beingintroduced from the heaters 23.

A crucible 26 made of boron nitride (BN) is disposed inside the coretube 25. A material is placed inside the crucible 26 and the temperatureof the crucible is raised to prepare a melt 27. A substrate 10 to serveas a seed crystal is attached to a substrate holding member 28. In theapparatus shown in FIG. 4, a plurality of substrates 10 can be attachedto the substrate holding member 28. The substrate 10 is rotated by arotary motor 29 a. A stirring propeller 30 can be immersed in the melt27. The propeller 30 is rotated by a rotary motor 29 b. In the presentexample, a common rotary motor can be used since the atmosphere pressureis 10 atm or lower. However, an electromagnetic induction rotarymechanism is used under an atmosphere pressure exceeding 10 atm.Atmosphere gas (raw material gas) is supplied from a gas source 31. Thepressure of the atmosphere gas is adjusted by a pressure regulator 32.The atmosphere gas is fed into the furnace after impurities are removedtherefrom by a gas purification unit 33.

The following description is directed to a method of growing GaNcrystals.

(1) Predetermined amounts of Ga and Na to serve as a flux are weighedand then are placed inside a crucible. The Ga used may have a purity of99.9999% (six nine). The Na may be purified Na. Na can be purified asfollows: Na is heated to melt in a glove box, the inside of which hasbeen subjected to He substitution. Then for example, oxides emerging onthe surface layer are removed. Alternatively, Na may be purified by zonerefining. The purity of Na can be increased by melting and solidifyingNa repeatedly in a tube to allow impurities to deposit and then removingthem. An offcut seed crystal substrate is attached to the substrateholding member.

(2) In order to melt the raw material placed inside the crucible, thetemperature inside the electric furnace is raised to 900° C. and therebya melt of the raw material is prepared. At this stage, the seed crystalsubstrate is not placed inside the crucible. In order to mix Ga and Na,the melt is stirred for several hours with the propeller being immersedin the melt. The atmosphere gas is, for instance, nitrogen gas or gascontaining ammonia. The pressure of the nitrogen gas is set at about 1atm to prevent Ga and Na from reacting with nitrogen gas at this stage.When ammonia is contained, the reaction occurs at lower pressure. Hence,it is preferable that the nitrogen gas alone is used for the atmospheregas at this stage.

(3) Next, the temperature of the crucible is set at 800° C. to bring themelt into a supersaturation state. In addition, the. atmosphere pressureis increased. In the present example, the atmosphere is, for example,nitrogen gas alone and is set at 50 atm. Subsequently, the seed crystalsubstrate is lowered to a position just above the surface of the meltand its temperature is made to approach the temperature of the melt.After several minutes, the seed crystal substrate is put into the meltto allow GaN crystals to start growing.

(4) During the crystal growth, the substrate is rotated at a rotationalspeed in a range of 10 rpm to 200 rpm. Desirably, the substrate isrotated at around 100 rpm. After the crystals are grown for 24 hours,the substrate is lifted to a position that is away from the surface ofthe melt by 5 to 10 mm. After being lifted, the substrate is rotated ata rotational speed of 300 rpm to 1500 rpm (desirably, around 1000 rpm)in order to remove the melt remaining on the substrate surface.Thereafter, the substrate including GaN single crystals thus grown istaken out of the chamber. During the crystal growth, the temperature ofthe crucible may be kept constant. However, the temperature of the meltmay be lowered at a constant rate to keep the supersaturation of themelt constant.

In the present invention, an offcut substrate was used as a seedcrystal. Hence, abnormal growth can be prevented from occurring duringthe crystal growth. Furthermore, a substrate with higher surfaceflatness can be obtained as compared to the case of using a common seedcrystal substrate. Generally, steps (steps composed of concavities andconvexities) oriented at random are present at the surface of GaNdeposited as in the above. Consequently, crystal growth proceeds fromrespective portions of the steps at random and thereby raised parts likehillocks and facets appear at the surface. As a result, abnormal crystalgrowth (hillock or island growth) occurs. In the present example, theuse of the offcut substrate shown in FIG. 2 allows the direction anddensity of the steps to be controlled to achieve stable two-dimensionalcrystal growth.

FIGS. 1A and 1B show typical surface morphological shapes obtained inthe case where LPE growth actually is carried out on. a substrate havingno slope with respect to its C-plane while FIGS. 1C and 1D show thoseobtained in the case where crystal growth is carried out on an offcutsubstrate. The use of a seed crystal layer that is parallel to theC-axis results in hexagonal island growth (three-dimensional growth)(FIGS. 1A(surface) and 1B(cross section). On the other hand, when usinga seed crystal layer offcut from the C-axis, crystals can grow that havea stepped surface and a surface morphology in which macroscopically theentire surface is lustrous (FIGS. 1C(surface) and 1D(cross section)).

In addition, as shown in FIGS. 1A and 1B, in the crystals formed throughthe island growth, carrier concentrations vary in a crystal planeconsiderably, for instance, by about two orders of magnitude withrespect to a desired carrier concentration. This is because, in the caseof the island growth, crystals grow on not only C-planes but also sidefaces thereof (lateral growth). Hence, conceivably, the variations arecaused because the planes other than the C-planes have highercoefficients of impurity incorporation. Furthermore, it also isconceivable that the variations are caused because the surface isprovided with very large concavities and convexities due to thedevelopment of large hexagonal islands and thereby great variations inthe state of diffusion of the impurities contained in the solution occurat the solid-liquid interface. The sizes of the hexagonal islands areabout 1 to 5 μm.

On the other hand, when using an offcut substrate (FIGS. 1C and 1D), itwas possible to limit the variations in in-plane carrier concentrationwithin one order of magnitude with respect to the desired value, i.e.within a range of one fifth to five times the desired value.Accordingly, the variations in in-plane carrier concentration werereduced considerably by using an offcut substrate particularly whencrystals are grown from the liquid phase. Conceivably, this is caused asfollows. The use of the offcut substrate makes the lateral growthdominate and thereby the growth faces are specified, which mainlyresults in a relatively constant amount of impurities to beincorporated. Furthermore, since the surface is relatively flat,considerably large concave portions are not produced. Consequently,variations in the state of diffusion of the impurities contained in thesolution are not caused at the solid-fluid interface.

Furthermore, it was confirmed that the growth rate improved by about 10%to 100% when using the offcut substrate. Conceivably, this is becausewhen Group III nitride crystals are grown by the LPE method, the lateralgrowth dominates (indicated with an arrow in FIG. 1D) although itdepends on the growth condition, and further the use of the offcutsubstrate allows this effect to manifest itself more noticeably.

GaN crystals were produced by the method described above and then weresubjected to measurements of dislocation density and PL intensity. Theyhad a dislocation density of 1×10² cm⁻² or lower. The spectrum of the PLintensity is shown in FIG. 5B. The intensity obtained at the peak around360 nm of the spectrum shown in FIG. 5B was 22 V. FIG. 5A shows the PLintensity of a GaN thin film produced by a general MOCVD method forcomparison. In this connection, FIGS. 5A and 5B show spectrums measuredwith slits having different widths from each other, respectively. Thepeak intensity obtained around 360 nm of the spectrum shown in FIG. 5Awas 0.48 V. The crystals obtained by the method of the present inventionhad a PL intensity that was about fifty times higher than that of thecrystals produced by a conventional method.

The growth of a GaN thick film carried out by a general HVPE method isconducted at a high temperature, specifically at 1050° C. In thepresent. invention, since crystal growth can be carried out at a lowtemperature, specifically at 800° C., the warping of a wafer caused by adifference in coefficient of linear expansion between the sapphiresubstrate and the crystals grown thereon can be reduced.

The present example used a flux containing Na alone. However, similareffects can be obtained even when using a mixed flux containingalkaline-earth metal such as, for example, Ca and a Li, Na, or K flux.For instance, when using a mixed flux containing Na and Ca, the Ca mixedto account for about 10% of the whole allows crystals to grow at lowerpressure.

In the present example, the description was directed to the manufactureof a GaN single crystal substrate using gallium. However, it isdesirable to manufacture a substrate having low absorptivity withrespect to a wavelength used in an optical device to be formed on thesubstrate. Hence, it is preferable that in a substrate for a lightemitting diode or a semiconductor laser handling light within theultraviolet region there are formed Al_(x)Ga_(1−x)N (wherein 0≦x≦1)single crystals that contain a large amount of Al and have lowabsorptivity with respect to light with short wavelengths. In thepresent invention, it also is possible to substitute a part of Ga byanother Group III element to form such Group III nitride semiconductorsingle crystals.

The best effect of the present invention is that abnormal growth isinhibited and thereby a Group III nitride semiconductor single crystalsubstrate having low dislocation density and a flat surface can beobtained by a highly mass-produced method. Particularly, in the LPEgrowth, hexagonal island growth is prevented from occurring, which makesit possible to improve the uniformity of the in-plane carrierconcentration and the growth rate. That is, according to the presentinvention, a substrate that allows a highly-reliable device to bemanufactured can be provided at low cost. Particularly, the flatsubstrate with a low dislocation density can facilitate the process ofmanufacturing a device such as a semiconductor laser throughhomoepitaxial growth and allows a device to be manufactured with a highyield.

Example 2

Group III nitride substrates with four different off angles wereobtained in the same manner as in Example 1 expect that crystals weregrown using seed substrates whose offcut angles were 0.05°, 0.1°, 0.3°,and 0.5°, respectively.

Comparative Example 1

Group III nitride substrates with two different offcut angles wereobtained in the same manner as in Example 1 expect that crystals weregrown using seed substrates whose offcut angles were 0.0°, and 0.03°,respectively.

With respect to the Group III nitride substrates thus obtained accordingto Example 2 and Comparative Example 1, the relationship between theoffcut angle of the seed substrate and the growth rate as well as.variations in in-plane carrier concentration was examined. Table 1 showsthe results. The carrier concentration was measured by theaforementioned method. This also applies to the examples describedbelow.

As shown in Table 1, when the offcut angle was 0.05° or larger, anincrease in growth rate of about 10% was observed and the variations incarrier concentration were reduced.

Furthermore, when the offcut angle was about 0.5°, the growth rate washigher than twice that of just the substrate, and the variations incarrier concentration were within one order of magnitude with respect toa carrier concentration mean value (i.e. one fifth to five times themean value) (in this case, 5×10¹⁷).

On the other hand, when the offcut angle was about 0.03°, no differencewas found as compared to the just substrate (whose offcut angle was0.0°).

The improvement in growth rate is particularly effective for thereduction in growth time in the case of using a thick film as asubstrate employed for producing a device. In addition, the improvementin uniformity of in-plane carrier concentration is importantparticularly for the uniformity of device characteristics. TABLE 1Offcut Growth Rate Variations in in-plane carrier Angle (μm/hr)concentration of wafer Example 2 0.05 20 ⅕ - Mean Value - 5 times 0.1 25⅕ - Mean Value - 5 times 0.3 35 ⅓ - Mean Value - 3 times 0.5 40 ⅓ - MeanValue - 3 times Comparative 0.0 18   1/10 - Mean Value - 10 timesExample 1 0.03 18   1/10 - Mean Value - 10 times

Example 3

An example of the present invention in which the offcut angle further isincreased is described with reference to FIGS. 6A to 6F. In thisexample, a C-plane sapphire substrate 31 was used as a substrate. GaN 32was grown on the sapphire substrate 31 by the MOCVD method to have athickness of 30 μm. Next, the GaN 32 was subjected to themechanochemical polishing to have an offcut angle of 0.5°. At thisstage, the substrate had a size of 20 mm×20 mm. Subsequently, using a Naflux as in Example 1, GaN 33 was grown on the substrate for 95 hours tohave a thickness of 1.9 mm (at a growth rate of 20 μm/hr). Further,polishing was carried out for a second time to obtain an offcut angle of5°. On the above-mentioned substrate with an offcut angle of 5° therefurther was grown GaN 34 by LPE to have a thickness of 100 μm (for about2.5 hours at a growth rate of 40 μm/hr). Thus, crystals were obtainedthat have high flatness and a surface at which hexagonal facets hardlywere found after the completion of the LPE due to the effect of theoffcut angle. Finally, the crystal surface was subjected to themechanochemical polishing and thus a final Group III nitride substratewas obtained. In this case, an excellent Group III nitride substrate wasobtained in which the variations in carrier concentration were within arange of one third to three times a carrier concentration mean value of1×10¹⁸.

In this case, the Group III nitride substrate was completed with thesapphire substrate included therein. However, it also was possible toremove the sapphire substrate 31 by polishing to provide aself-supported substrate as required.

Example 4

In this example, the description is directed to the case where an offcutsubstrate is produced using a temperature gradient or concentrationgradient with reference to FIGS. 7A to 7D and FIG. 8.

A substrate 31 and the method of producing a substrate 32 shown in FIGS.7A to 7D are identical to those used in Example 3.

Using a growth furnace installed in an electric furnace having two zoneslike the one shown in FIG. 8, the LPE growth was carried out withtemperature gradient being provided inside the electric furnace. In FIG.8, numeral 81 indicates a substrate, numeral 82 a solution, numeral 83an upper heater, and numeral 84 a lower heater.

A sample with a shape shown in FIG. 7C was placed in a crucible as shownin FIG. 8 and thereby a GaN thick film 33 was grown.

After a growth time of 100 hours, crystals were obtained that had anoffcut angle of 2° and a thickness of about 2 mm. In this case, thecrystals thus obtained had lustrous and excellent surface morphology andthus relatively favorable crystals were obtained in which hexagonalisland growth hardly was caused. The surface of the crystals thusobtained was subjected to the mechanochemical polishing and thenvariations in in-plane carrier concentration were determined. As aresult, the variations were within one order of magnitude of thein-plane carrier concentration mean value.

Example 5

In Example 5, the description is directed to an example of a method ofmanufacturing a semiconductor laser using a substrate obtained inExample 1. FIG. 9 shows the configuration of a semiconductor laser 90.

First, on a substrate 91 obtained in the above-mentioned example isformed a contact layer 92 of n-type GaN doped with Si so as to have acarrier concentration of 5×10¹⁸ or lower. The self-supported substrate91 is a substrate obtained in Example 1 by removing a sapphire substrateon a back surface from an offcut substrate on which Group III nitridecrystals are formed and polishing the back surface so as to be parallelto a front surface. Incidentally, it is not always necessary to removethe sapphire substrate on the back surface. In GaN-based crystals(crystals containing Ga and N), when Si is added thereto as an impurity,holes present in Ga increase in number. Since the holes present in Gadiffuse easily, they have harmful effects in terms of, for example,lifetime when a device is formed on the contact layer. Hence, the dopingamount is controlled so that the contact layer has a carrierconcentration of 3×10¹⁸ or lower.

Next, on the contact layer 92 are formed a cladding layer 93 of n-typeAl_(0.07)Ga_(0.93)N and a light guiding layer 94 of n-type GaN.

Subsequently, as an active layer 95 there is formed a multiple quantumwell (MQW) composed of a well layer (with a thickness of about 3 nm)made of Ga_(0.8)In_(0.2)N and a barrier layer (with a thickness of about6 nm) made of GaN. Thereafter, on the active layer 95 are formedsequentially a light guiding layer 96 of p-type GaN, a cladding layer 97of p-type. Al_(0.07)Ga_(0.93)N, and a contact layer 98 of p-type GaN.These layers can be formed by well-known methods. The semiconductorlaser 90 is of a double-hetero junction type. The energy gap of the welllayer containing indium in the MQW active layer is smaller than those ofthe n-type and p-type cladding layers containing aluminum. On the otherhand, the highest optical refractive index is obtained in the well layerof the active layer 95, while the light guiding layers and the claddinglayers have optical refractive indices that decrease in this order.

On the contact layer 98 there is formed an insulating film 99 forming acurrent injection region having a width of about 2 μm. A ridge part toserve as a current constriction part is formed in the upper portion ofthe p-type cladding layer 97 and the p-type contact layer 98.

On the upper side of the p-type contact layer 98 there is formed ap-side electrode 100 that is in ohmic contact with the contact layer 98.The p-side electrode 100 may be formed of a layered product of nickel(Ni) and gold (Au).

On the n-type contact layer 92 is formed an n-side electrode 101 that isin ohmic contact with the contact layer 92. The n-side electrode 101 maybe formed of a layered product of titanium (Ti) and aluminum (Al).

The semiconductor laser produced by the method described above wassubjected to a device evaluation. When a predetermined forward voltagewas applied between the p-side electrode and the n-side electrode of thesemiconductor laser obtained in the above, positive holes and electronsare injected into the MQW active layer from the P-side electrode and then-side electrode, respectively, to be recombined with each other in theMQW active layer and thereby an optical gain was produced. Consequently,the semiconductor laser generated oscillation with an emissionwavelength of 404 nm.

In the semiconductor laser of the present example, a substrate with alow dislocation density, specifically, 1×10² cm⁻² or lower, was used asits substrate. Accordingly, the semiconductor laser had a lowerthreshold, improved luminous efficiency, and improved reliability ascompared to one produced on a GaN substrate with a high dislocationdensity.

Furthermore, it also is possible to produce a GaN substrate by removingthe sapphire part other than the GaN crystals by, for instance,polishing, and then to produce a device thereon.

Using a substrate obtained by the manufacturing method of the presentinvention, Group III nitride crystals are grown epitaxially on thesubstrate, and thereby a semiconductor device is obtained that includesa semiconductor element such as a LD or LED.

As described above, according to the manufacturing method of the presentinvention, a substrate can be manufactured easily that includes GroupIII nitride crystals having excellent characteristics.

The invention may be embodied in other forms without departing from thespirit or essential characteristics thereof The embodiments disclosed inthis application are to be considered in all respects as illustrativeand not limiting. The scope of the invention is indicated by theappended claims rather than by the foregoing description, and allchanges which come within the meaning and range of equivalency of theclaims are intended to be embraced therein.

1-5. (canceled)
 6. A method of manufacturing a Group III nitridesubstrate, the method comprising: (i) forming a semiconductor layer on asubstrate, the semiconductor layer being formed of a semiconductorexpressed by a composition formula of Al_(u)Ga_(v)In_(1−u−v)N (wherein0≦u ≦1 and 0≦v≦1) and having a (0001) plane present at its surface; (ii)processing the surface of the semiconductor layer so that the surfacebecomes a plane sloped with respect to the (0001) plane of thesemiconductor layer; and (iii) bringing the surface of the semiconductorlayer into contact with a melt containing a solvent and at least oneGroup III element selected from gallium, aluminum, and indium, in anatmosphere containing nitrogen, to make the at least one Group IIIelement and the nitrogen react with each other to grow Group III nitridecrystals on the semiconductor layer.
 7. The method of manufacturing aGroup III nitride substrate according to claim 6, wherein the at leastone Group III element is gallium, and the Group III nitride crystals aregallium nitride.
 8. The method of manufacturing a Group III nitridesubstrate according to claim 6, wherein the Group III nitride crystalsare grown on the semiconductor layer at a growth rate of at least 20μm/hr.
 9. The method of manufacturing a Group III nitride substrateaccording to claim 6, wherein the Group III nitride crystals that havegrown on the semiconductor layer have variations in in-plane carrierconcentration, the variations being within a range of one fifth to fivetimes a carrier concentration mean value.
 10. The method ofmanufacturing a Group III nitride substrate according to claim 6,wherein the atmosphere containing nitrogen is a pressure atmosphere. 11.The method of manufacturing a Group III nitride substrate according toclaim 6, wherein the solvent is alkali metal.
 12. The method ofmanufacturing a Group III nitride substrate according to claim 6,wherein the solvent contains alkali metal and alkaline-earth metal. 13.The method of manufacturing a Group III nitride substrate according toclaim 11, wherein the alkali metal is at least one selected from a groupconsisting of sodium, lithium, and potassium.
 14. The method ofmanufacturing a Group III nitride substrate according to claim 6,wherein in the process (ii), the surface of the semiconductor layer isprocessed by polishing.
 15. The method of manufacturing a Group IIInitride substrate according to claim 6, wherein the processes (i) and(ii) are carried out simultaneously.
 16. The method of manufacturing aGroup III nitride substrate according to claim 15, wherein the processes(i) and (ii) are carried out using temperature gradient provided duringcrystal growth.
 17. The method of manufacturing a Group III nitridesubstrate according to claim 6, wherein the substrate is made ofsapphire. 18-19. (canceled)